一种适用于复杂异相体系中羟基自由基定量检测的探针分子—香豆素

doi:10.7503/cjcu20180364

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (12): 2658.doi: 10.7503/cjcu20180364

一种适用于复杂异相体系中羟基自由基定量检测的探针分子—香豆素

韩瑞霞^1,², 吕继涛¹(), 张淑贞^1,²

1. 中国科学院生态环境研究中心, 环境化学与生态毒理学国家重点实验室, 北京 100085
2. 中国科学院大学, 北京 100049

收稿日期:2018-05-16 出版日期:2018-11-15 发布日期:2018-11-15
作者简介:
联系人简介: 吕继涛, 男, 博士, 助理研究员, 主要从事环境界面化学方面的研究. E-mail: jtlv@rcees.ac.cn
基金资助:
国家自然科学基金(批准号: 21537005, 41773119, 21621064)和国家“九七三”计划项目(批准号: 2014CB441102)资助.

Molecular Probe for the Determination of Hydroxyl Radicals in Heterogeneous Systems: Coumarin^†

HAN Ruixia^1,², LÜ Jitao^1,^*(), ZHANG Shuzhen^1,²

1. State Key Laboratory of Environmental Chemistry and Ecotoxicology,Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences, Beijing 100085, China
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2018-05-16 Online:2018-11-15 Published:2018-11-15
Contact: LÜ Jitao E-mail:jtlv@rcees.ac.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21537005, 41773119, 21621064) and the National Program on Key Basic Research Project of China(No.2014CB441102).

摘要/Abstract

摘要：

系统比较了3种定量检测羟基自由基(·OH)的探针分子对苯二甲酸二钠(TPA)、苯甲酸钠(BA)和香豆素(COU), 相应的转化产物分别为2-羟基对苯二甲酸(hTPA)、 2-羟基苯甲酸(SA)和7-羟基香豆素(7-hCOU). 结果表明, 最常用的TPA和BA的转化产物在水铁矿表面存在明显的吸附, 最大吸附量分别为2.49和2.09 mg/g, 因而不适合作为复杂矿物体系的探针分子. 就探针分子对·OH的响应灵敏度、响应线性及线性范围而言, COU的表现明显优于TPA和BA, 并且7-hCOU的检测限与hTPA和SA相仿(分别为0.005, 0.046和0.072 μmol/L). 通过COU在微生物-矿物体系还原-氧化循环过程及土壤/沉积物还原-氧化过程中对·OH测定的应用, 进一步验证了该探针分子用于·OH定量检测的稳定性和重现性. 因此, COU可作为复杂异相体系中·OH定量检测的探针分子. 值得注意的是, pH对·OH的产生影响极大, 因此在比较不同体系间·OH产量时应注意使其处于相同的pH缓冲液中以排除干扰.

关键词: 羟基自由基, 荧光探针, 香豆素, 微生物-矿物

Abstract:

Three common molecular probes—disodium terephthalate(TPA), sodium benzoate(BA) and coumarin(COU), with the corresponding transformation products of which are 2-hydroxyterephthalic acid(hTPA), salicylic acid(SA) and 7-hydroxycoumarin(7-hCOU) were assessed, respectively. The results showed that transformation products of TPA and BA were adsorbed seriously on ferrihydrite(the maximum adsorption capacity were 2.49 and 2.09 mg/g, respectively), which made them unsuitable to be used in heterogeneous systems. Moreover, COU was much better than TPA and BA in terms of sensitivity, linearity and concentration range responded to ·OH. And 7-hCOU had lower limit of detection than hTPA and SA(0.005, 0.046 and 0.072 μmol/L, respectively). COU was further demonstrated to be capable of quantifying ·OH produced in microbe-mineral systems and soil and sediment systems during redox cycle, where it showed great stability and reproducibility. It proved to be a reasonable molecular probe to apply to other ·OH production processes in heterogeneous systems and natural environment. Notably, it should be in the same pH buffer when comparing ·OH concentration between different systems since the pH has a great influence on the ·OH production.

Key words: Hydroxyl radical, Fluorescence probe, Coumarin, Microbe-mineral

中图分类号:

O657.3

TrendMD:

韩瑞霞, 吕继涛, 张淑贞. 一种适用于复杂异相体系中羟基自由基定量检测的探针分子—香豆素. 高等学校化学学报, 2018, 39(12): 2658.

HAN Ruixia,LÜ Jitao,ZHANG Shuzhen. Molecular Probe for the Determination of Hydroxyl Radicals in Heterogeneous Systems: Coumarin^†. Chem. J. Chinese Universities, 2018, 39(12): 2658.

图/表 6

Fig.1 Reactions between three molecular probes[TPA(A), BA(B), COU(C)] and hydroxyl radicals(D), adsorption of salicylic acid structure on iron oxides

Fig.2 Adsorption of molecular probes and their products on ferrihydrite(A) TPA; (B) BA; (C) COU; (D) hTPA; (E) SA; (F) 7-hCOU.

Fig.3 Calibration curves of molecular probes(A) and transformation products(B)

Fig.4 Quantification of hydroxyl radicals produced by Fenton reactions with three molecular probes(A) hTPA; (B) SA; (C) 7-hCOU.

Fig.5 Production of ferrous ions(A) and hydroxyl radicals(B) in microbe-ferrihydrite system during the redox cycle

Fig.6 Concentration of ·OH determined by coumarin(A) and relative intensity of DMPO-OH detected with ESR(B)a. GSD-4+3 mmol/L H2O2+100 mmol/L DMPO; b. GSS-7+3 mmol/L H2O2+100 mmol/L DMPO; c. GSD-6+3 mmol/L H2O2+100 mmol/L DMPO; d. GSD-4+3 mmol/L H2O2+100 mmol/L DMPO+5%(volume fraction)DMSO; e. GSD-4+100 mmol/L DMPO produced in the oxidation of chemically-reduced soil(GSS-7) and sediments(GSD-4, GSD-6).

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一种适用于复杂异相体系中羟基自由基定量检测的探针分子—香豆素

Molecular Probe for the Determination of Hydroxyl Radicals in Heterogeneous Systems: Coumarin^†

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一种适用于复杂异相体系中羟基自由基定量检测的探针分子—香豆素

Molecular Probe for the Determination of Hydroxyl Radicals in Heterogeneous Systems: Coumarin†

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Molecular Probe for the Determination of Hydroxyl Radicals in Heterogeneous Systems: Coumarin^†